WO2017141735A1 - 固体電解質組成物、全固体二次電池用電極シートおよび全固体二次電池、並びに、全固体二次電池用電極シートおよび全固体二次電池の製造方法 - Google Patents

固体電解質組成物、全固体二次電池用電極シートおよび全固体二次電池、並びに、全固体二次電池用電極シートおよび全固体二次電池の製造方法 Download PDF

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WO2017141735A1
WO2017141735A1 PCT/JP2017/004029 JP2017004029W WO2017141735A1 WO 2017141735 A1 WO2017141735 A1 WO 2017141735A1 JP 2017004029 W JP2017004029 W JP 2017004029W WO 2017141735 A1 WO2017141735 A1 WO 2017141735A1
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Prior art keywords
solid electrolyte
active material
sulfide
secondary battery
solid
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PCT/JP2017/004029
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English (en)
French (fr)
Japanese (ja)
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洋史 加賀
宏顕 望月
智則 三村
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富士フイルム株式会社
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Priority to EP17752997.1A priority Critical patent/EP3419098B1/de
Priority to CN201780005815.0A priority patent/CN108475817B/zh
Priority to KR1020187022413A priority patent/KR102126144B1/ko
Priority to JP2018500039A priority patent/JP6721669B2/ja
Publication of WO2017141735A1 publication Critical patent/WO2017141735A1/ja
Priority to US16/019,963 priority patent/US10818967B2/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/10—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances sulfides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H01M4/623—Binders being polymers fluorinated polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a solid electrolyte composition, an electrode sheet for an all-solid secondary battery and an all-solid secondary battery, and an electrode sheet for an all-solid secondary battery and an all-solid secondary battery manufacturing method.
  • a lithium ion secondary battery is a storage battery that has a negative electrode, a positive electrode, and an electrolyte sandwiched between the negative electrode and the positive electrode, and can be charged and discharged by reciprocating lithium ions between the two electrodes.
  • an organic electrolytic solution has been used as an electrolyte in a lithium ion secondary battery.
  • the organic electrolyte is liable to leak, and there is a possibility that a short circuit occurs inside the battery due to overcharge and overdischarge, resulting in ignition, and further improvements in reliability and safety are required. Under such circumstances, an all-solid secondary battery using an inorganic solid electrolyte instead of an organic electrolyte has been attracting attention.
  • All-solid-state secondary batteries are composed of a solid negative electrode, electrolyte, and positive electrode, which can greatly improve safety and reliability, which is a problem of batteries using organic electrolytes, and can also extend the life. It will be. Furthermore, the all-solid-state secondary battery can have a structure in which electrodes and an electrolyte are directly arranged in series. Therefore, it is possible to increase the energy density as compared with a secondary battery using an organic electrolyte, and application to an electric vehicle, a large storage battery, and the like is expected.
  • Patent Document 1 describes an all-solid-state secondary battery including a solid electrolyte obtained by surface-modifying a glass ceramic solid electrolyte with a glass solid electrolyte.
  • Patent Document 2 discloses an active material, a first solid electrolyte material that is in contact with the active material, has an anion component different from the anion component of the active material, and is a single-phase electron-ion mixed conductor; All solids comprising an electrode active material layer in contact with the first solid electrolyte material and having the same anion component as the first solid electrolyte material and a second solid electrolyte material that is an ionic conductor having no electronic conductivity A battery is described.
  • Patent Documents 1 and 2 also disclose the use of sulfide-based inorganic solid electrolytes.
  • the sulfide-based inorganic solid electrolyte is highly reactive, and deteriorates itself during the charge / discharge process, thereby reducing battery performance including cycle characteristics.
  • this problem has not been sufficiently solved, and when a sulfide-based inorganic solid electrolyte is used, further study is required to improve cycle characteristics.
  • an object of the present invention is to provide a solid electrolyte composition used for an all-solid secondary battery, which can improve the cycle characteristics of the all-solid secondary battery. Moreover, this invention makes it a subject to provide the electrode sheet for all-solid-state secondary batteries and the all-solid-state secondary battery using the said solid electrolyte composition. Furthermore, this invention makes it a subject to provide the manufacturing method of each electrode sheet for all-solid-state secondary batteries, and all-solid-state secondary batteries.
  • the inventors of the present invention are a sulfide-based inorganic solid electrolyte (first sulfide-based inorganic solid electrolyte) containing an active material and a halogen element that is in contact with the active material, and is at least partly A solid containing a sulfide-based inorganic solid electrolyte having a crystalline phase and a sulfide-based inorganic solid electrolyte (second sulfide-based inorganic solid electrolyte) having a composition different from that of the first sulfide-based inorganic solid electrolyte It has been found that the all solid state secondary battery produced using the electrolyte composition is excellent in cycle characteristics. The present invention has been further studied based on these findings and has been completed.
  • an active material a first sulfide-based inorganic solid electrolyte, and a second sulfide-based inorganic solid electrolyte having a composition different from that of the first sulfide-based inorganic solid electrolyte, the first sulfide
  • the active material is a positive electrode active material.
  • the active material is a negative electrode active material.
  • L represents at least one selected from the group consisting of Li, Na and K.
  • M represents at least one selected from the group consisting of Al, Ga, In, Si, Ge, Sn, P, As, Ti, Zr, V, Nb, and Ta.
  • Y represents at least one selected from the group consisting of O, S and Se. However, it includes at least S to component represented by Y b.
  • X represents at least one selected from the group consisting of Cl, Br and I. 2 ⁇ a ⁇ 12, 2 ⁇ b ⁇ 8, and 0 ⁇ c ⁇ 5.
  • X is at least one selected from the group consisting of Cl, Br and I, and 0 ⁇ x ⁇ 2.
  • ⁇ 6> The solid electrolyte composition according to ⁇ 4> or ⁇ 5>, wherein X contains at least one selected from the group consisting of Cl and Br.
  • ⁇ 7> The solid electrolyte composition according to any one of ⁇ 1> to ⁇ 6>, containing a binder.
  • ⁇ 8> The solid electrolyte composition according to ⁇ 7>, wherein the binder has a particle shape.
  • ⁇ 9> The solid electrolyte composition according to ⁇ 7> or ⁇ 8>, wherein the binder is acrylic latex, urethane latex and / or urea latex.
  • An electrode sheet for an all-solid-state secondary battery having a layer of the solid electrolyte composition according to any one of ⁇ 1> to ⁇ 9> on a current collector.
  • An all-solid secondary battery comprising a positive electrode active material layer, a negative electrode active material layer, and an inorganic solid electrolyte layer, wherein at least one of the positive electrode active material layer and the negative electrode active material layer comprises ⁇ 1> to ⁇ 9
  • An all-solid secondary battery that is a layer of the solid electrolyte composition according to any one of the above.
  • the method for producing an electrode sheet for an all-solid-state secondary battery according to ⁇ 10> including the following steps.
  • a method for producing an all-solid-state secondary battery comprising producing an all-solid-state secondary battery via the method for producing an electrode sheet for an all-solid-state secondary battery according to ⁇ 12>.
  • a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • acryl or “(meth) acryl” is simply described, it means methacryl and / or acryl.
  • the solid electrolyte composition of the present invention has an excellent effect that good cycle characteristics can be realized when used for the production of an all-solid secondary battery.
  • the electrode sheet for all-solid-state secondary batteries and all-solid-state secondary batteries of this invention utilize the solid electrolyte composition which has said outstanding effect, and show the outstanding performance.
  • the electrode sheet for all-solid-state secondary batteries and all-solid-state secondary battery of this invention can each be manufactured suitably.
  • FIG. 1 is a longitudinal sectional view schematically showing an all solid state secondary battery according to a preferred embodiment of the present invention.
  • FIG. 2 is a longitudinal sectional view schematically showing an all-solid secondary battery (coin battery) produced in the example.
  • the solid electrolyte composition of the present invention includes an active material, a first sulfide-based inorganic solid electrolyte, and a second sulfide-based inorganic solid electrolyte, which will be described later. Hereinafter, preferred embodiments thereof will be described. First, an all-solid secondary battery using the solid electrolyte composition of the present invention will be described.
  • the all solid state secondary battery of the present invention has a positive electrode, a negative electrode facing the positive electrode, and a solid electrolyte layer between the positive electrode and the negative electrode.
  • the positive electrode has a positive electrode active material layer on a positive electrode current collector.
  • the negative electrode has a negative electrode active material layer on a negative electrode current collector.
  • At least one of the negative electrode active material layer and the positive electrode active material layer is formed of the solid electrolyte composition of the present invention.
  • the negative electrode active material layer and the positive electrode active material layer are formed of the solid electrolyte composition of the present invention. It is preferable.
  • the active material layer formed of the solid electrolyte composition is preferably the same as that in the solid content of the solid electrolyte composition with respect to the component species to be contained and the content ratio thereof.
  • preferred embodiments of the present invention will be described, but the present invention is not limited thereto.
  • FIG. 1 is a cross-sectional view schematically showing an all solid state secondary battery (lithium ion secondary battery) according to a preferred embodiment of the present invention.
  • the all-solid-state secondary battery 10 according to this embodiment includes a negative electrode current collector 1, a negative electrode active material layer 2, a solid electrolyte layer 3, a positive electrode active material layer 4, and a positive electrode current collector 5 stacked in this order as viewed from the negative electrode side.
  • the adjacent layers are in direct contact with each other.
  • the all solid state secondary battery having the layer configuration of FIG. 1 may be referred to as an all solid state secondary battery sheet.
  • both the positive electrode active material layer and the negative electrode active material layer are formed of the solid electrolyte composition of the present invention.
  • the solid electrolyte layer 3 usually does not contain a positive electrode active material and / or a negative electrode active material.
  • the positive electrode active material layer 4 and the negative electrode active material layer 2 each include at least one positive electrode active material or negative electrode active material. Furthermore, the positive electrode active material layer 4 and the negative electrode active material layer 2 contain an inorganic solid electrolyte. When the active material layer contains an inorganic solid electrolyte, the ionic conductivity can be improved.
  • the inorganic solid electrolyte contained in the positive electrode active material layer 4, the solid electrolyte layer 3, and the negative electrode active material layer 2 may be the same or different.
  • either or both of the positive electrode active material layer and the negative electrode active material layer may be simply referred to as an active material layer or an electrode active material layer.
  • One or both of the positive electrode active material and the negative electrode active material may be simply referred to as an active material or an electrode active material.
  • the thicknesses of the positive electrode active material layer 4, the solid electrolyte layer 3, and the negative electrode active material layer 2 are not particularly limited. Considering general battery dimensions, the thickness of each of the above layers is preferably 10 to 1,000 ⁇ m, more preferably 20 ⁇ m or more and less than 500 ⁇ m. In the all solid state secondary battery of the present invention, it is more preferable that the thickness of at least one of the positive electrode active material layer 4, the solid electrolyte layer 3 and the negative electrode active material layer 2 is 50 ⁇ m or more and less than 500 ⁇ m.
  • the positive electrode current collector 5 and the negative electrode current collector 1 are preferably electronic conductors. In the present invention, either or both of the positive electrode current collector and the negative electrode current collector may be simply referred to as a current collector.
  • Materials for forming the positive electrode current collector include aluminum, aluminum alloy, stainless steel, nickel, titanium, etc., as well as the surface of aluminum or stainless steel treated with carbon, nickel, titanium, or silver (forming a thin film) Among them, aluminum and aluminum alloys are more preferable.
  • the material for forming the negative electrode current collector is treated with carbon, nickel, titanium, or silver on the surface of aluminum, copper, copper alloy, stainless steel. What was made to do is preferable, and aluminum, copper, a copper alloy, and stainless steel are more preferable.
  • the current collector is usually in the form of a film sheet, but a net, a punched one, a lath, a porous body, a foam, a fiber group molded body, or the like can also be used.
  • the thickness of the current collector is not particularly limited, but is preferably 1 to 500 ⁇ m.
  • the current collector surface is roughened by surface treatment.
  • a functional layer, a member, or the like is appropriately interposed or disposed between or outside each of the negative electrode current collector, the negative electrode active material layer, the solid electrolyte layer, the positive electrode active material layer, and the positive electrode current collector. May be.
  • Each layer may be composed of a single layer or a plurality of layers.
  • the basic structure of the all-solid-state secondary battery can be manufactured by arranging each of the above layers. Depending on the application, it may be used as an all-solid secondary battery as it is, but in order to form a dry battery, it is further enclosed in a suitable housing.
  • the housing may be metallic or made of resin (plastic). In the case of using a metallic material, for example, an aluminum alloy or a stainless steel material can be used.
  • the metallic housing is preferably divided into a positive-side housing and a negative-side housing, and electrically connected to the positive current collector and the negative current collector, respectively.
  • the casing on the positive electrode side and the casing on the negative electrode side are preferably joined and integrated through a gasket for preventing a short circuit.
  • Solid electrolyte composition The solid electrolyte composition of the present invention is as described above, and will be specifically described below.
  • the solid electrolyte composition of the present invention contains at least two different types of sulfide-based inorganic solid electrolytes.
  • the sulfide-based inorganic solid electrolyte may be simply referred to as “inorganic solid electrolyte”.
  • the solid electrolyte composition of the present invention includes an active material and includes at least a first sulfide-based inorganic solid electrolyte and a second sulfide-based inorganic solid electrolyte. In the solid electrolyte composition of the present invention, the active material and the first sulfide-based inorganic solid electrolyte are in contact with each other.
  • the first sulfide-based inorganic solid electrolyte is preferably coated with an active material.
  • the solid electrolyte composition of the present invention may include an active material that is not in contact with each other and a first sulfide-based inorganic solid electrolyte.
  • the “solid electrolyte” of the inorganic solid electrolyte is a solid electrolyte capable of moving ions inside. Since it does not contain organic substances as the main ion conductive material, organic solid electrolytes (polymer electrolytes typified by polyethylene oxide (PEO), etc., organics typified by lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), etc. It is clearly distinguished from the electrolyte salt). Further, since the inorganic solid electrolyte is solid in a steady state, it is not dissociated or released into cations and anions.
  • organic solid electrolytes polymer electrolytes typified by polyethylene oxide (PEO), etc.
  • LiTFSI lithium bis (trifluoromethanesulfonyl) imide
  • inorganic electrolyte salts LiPF 6 , LiBF 4 , lithium bis (fluorosulfonyl) imide (LiFSI), LiCl, etc.
  • LiPF 6 lithium bis (fluorosulfonyl) imide
  • LiFSI lithium bis (fluorosulfonyl) imide
  • LiCl LiCl
  • the inorganic solid electrolyte is not particularly limited as long as it has conductivity of ions of metal elements belonging to Group 1 or Group 2 of the periodic table, and generally does not have electron conductivity.
  • the inorganic solid electrolyte preferably has an ionic conductivity of lithium ions.
  • inorganic solid electrolyte a solid electrolyte material usually used for an all-solid secondary battery can be appropriately selected and used.
  • Typical examples of inorganic solid electrolytes include (i) sulfide-based inorganic solid electrolytes and (ii) oxide-based inorganic solid electrolytes.
  • a sulfide-based inorganic solid electrolyte having high ionic conductivity is used.
  • the first sulfide-based inorganic solid electrolyte used in the present invention contains a halogen element, and at least a part thereof is a crystalline phase.
  • that at least a part of the first sulfide-based inorganic solid electrolyte is a crystalline phase means that diffraction peaks or lattice fringes derived from the crystal structure are observed by X-ray diffraction, a transmission electron microscope, or the like. means.
  • the first sulfide-based inorganic solid electrolyte contains a halogen element, the content of highly reactive sulfur element can be suppressed and good ion conductivity can be maintained.
  • the first sulfide-based inorganic solid electrolyte when at least a part of the first sulfide-based inorganic solid electrolyte is a crystalline phase, a better ion conduction path is formed in the electrode layer.
  • a first sulfide-based inorganic solid electrolyte that satisfies the above requirements and has excellent ion conductivity and reaction resistance is obtained by using a second sulfide-based inorganic solid having a composition different from that of the active material and the first sulfide-based inorganic solid electrolyte.
  • a solid interface of good quality is formed compared to the interface between the active material and the solid electrolyte in the conventional electrode layer, and excellent ionic conductivity is obtained.
  • the battery performance deterioration due to the high reactivity of the sulfur element is suppressed, and the contact state between the active material and the first sulfide-based inorganic solid electrolyte is maintained without depending on the pressure. Battery life can be extended (excellent cycle characteristics). Moreover, said effect is not exhibited when the 1st sulfide type inorganic solid electrolyte is used independently.
  • the first sulfide-based inorganic solid electrolyte used in the present invention is not particularly limited as long as it contains a halogen element and at least a part thereof is in a crystalline phase.
  • the first sulfide-based inorganic solid electrolyte contains sulfur element (S), has an ionic conductivity of a metal element belonging to Group 1 or Group 2 of the periodic table, and has an electronic insulating property. What has is preferable.
  • the first sulfide-based inorganic solid electrolyte preferably contains at least Li, S, and a halogen element and has lithium ion conductivity. However, depending on the purpose or case, other than Li, S, and a halogen element Other elements may be included. For example, a lithium ion conductive inorganic solid electrolyte satisfying the composition represented by the following formula (1) can be mentioned, which is preferable.
  • L represents at least one selected from the group consisting of Li, Na and K.
  • M represents at least one selected from the group consisting of Al, Ga, In, Si, Ge, Sn, P, As, Ti, Zr, V, Nb, and Ta.
  • Y represents at least one selected from the group consisting of O, S and Se. However, it includes at least S to component represented by Y b.
  • X represents at least one selected from the group consisting of Cl, Br and I. 2 ⁇ a ⁇ 12, 2 ⁇ b ⁇ 8, and 0 ⁇ c ⁇ 5.
  • the first sulfide-based inorganic solid electrolyte for example, a raw material composition containing Li 2 S, a sulfide of an element belonging to Groups 13 to 15 and a lithium halide is used. Can be mentioned.
  • Li 2 S—LiI—P 2 S 5 Li 2 S—LiI—Li 2 O—P 2 S 5 , Li 2 S—LiBr—P 2 S 5 , Li 2 S—LiBr—Li 2 O—P 2 S 5, Li 2 S-LiCl- P 2 S 5, Li 2 S-LiCl-Li 2 O-P 2 S 5, Li 2 S-LiI-Li 3 PO 4 -P 2 S 5, Li 2 S-LiBr- Li 3 PO 4 —P 2 S 5 , Li 2 S—LiCl—Li 3 PO 4 —P 2 S 5 , Li 2 S—LiCl—Li 3 PO 4 —P 2 S 5 , Li 2 S—LiBr—P 2 S 5 —P 2 O 5 , Li 2 S—LiI—P 2 S 5 —P 2 O 5 , Li 2 S—LiCl—P 2 S 5 —P 2 O 5 , Li 2 S—LiCl—P 2 S 5
  • the first sulfide-based inorganic solid electrolyte is more preferably represented by the following formula (2).
  • Li 7-x PS 6-x X x formula (2) In the formula (2), X is at least one selected from the group consisting of Cl, Br and I, and 0 ⁇ x ⁇ 2.
  • X preferably contains at least one selected from the group consisting of Cl and Br, and preferably 0 ⁇ x ⁇ 1.5. .
  • the first sulfide-based inorganic solid electrolyte can be produced by reaction of any one of the following [1] to [3] with lithium halide (LiX).
  • LiX lithium halide
  • Lithium sulfide and at least one of elemental phosphorus and elemental sulfur or
  • Lithium sulfide and sulfide Phosphorus for example, diphosphorus pentasulfide (P 2 S 5 )
  • simple phosphorus and simple sulfur simple phosphorus and simple sulfur.
  • the lithium ion conductivity is further increased by adjusting the ratio of Li, P, S and X so as to satisfy the formula (2).
  • the lithium ion conductivity can be preferably 1 ⁇ 10 ⁇ 4 S / cm or more, more preferably 1 ⁇ 10 ⁇ 3 S / cm or more. Although there is no particular upper limit, it is practical that it is 1 ⁇ 10 ⁇ 1 S / cm or less.
  • the second sulfide-based inorganic solid electrolyte is not particularly limited as long as the composition is different from that of the first sulfide-based inorganic solid electrolyte.
  • the difference in composition means that the type and / or ratio of elements constituting the first sulfide-based inorganic solid electrolyte and the type and / or ratio of elements constituting the second sulfide-based inorganic solid electrolyte , Means different.
  • the second sulfide-based inorganic solid electrolyte contains sulfur element (S), has an ionic conductivity of a metal element belonging to Group 1 or Group 2 of the periodic table, and has an electronic insulating property. What has is preferable.
  • the first sulfide-based inorganic solid electrolyte preferably contains at least Li and S as elements and has lithium ion conductivity. However, depending on the purpose or the case, other elements other than Li and S may be used. May be included. For example, a lithium ion conductive inorganic solid electrolyte that satisfies the composition represented by the following formula (A) can be mentioned and is preferable.
  • L represents an element selected from Li, Na and K, and Li is preferred.
  • M represents an element selected from B, Zn, Sn, Si, Cu, Ga, Sb, Al, P, Ge, In, As, V, Nb, Ta, Ti, and Zr. Among these, B, Sn, Si, Al, P or Ge is preferable, and Sn, Al, P or Ge is more preferable.
  • A represents I, Br, Cl or F, preferably I or Br, and particularly preferably I.
  • L, M, and A can each be one or more of the above elements.
  • a1 to d1 indicate the composition ratio of each element, and a1: b1: c1: d1 satisfies 1 to 12: 0 to 2: 2 to 12: 0 to 5.
  • a1 is further preferably 1 to 9, and more preferably 1.5 to 4.
  • b1 is preferably 0 to 1.
  • c1 is preferably 3 to 7, and more preferably 4 to 6.
  • d1 is preferably 0 to 3, more preferably 0 to 1.
  • composition ratio of each element can be controlled by adjusting the blending amount of the raw material compound in producing the second sulfide-based inorganic solid electrolyte, as will be described later.
  • the second sulfide-based inorganic solid electrolyte may be amorphous (glass) or crystallized (glass ceramic), or only part of it may be crystallized.
  • Li—PS system glass containing Li, P, and S or Li—PS system glass ceramics containing Li, P, and S can be used.
  • the second sulfide-based inorganic solid electrolyte includes [1] lithium sulfide (Li 2 S) and phosphorus sulfide (for example, diphosphorus pentasulfide (P 2 S 5 )), [2] lithium sulfide, simple phosphorus and simple sulfur. It can be produced by reaction of at least one of [3] lithium sulfide, phosphorus sulfide (for example, diphosphorus pentasulfide (P 2 S 5 )), simple phosphorus and simple sulfur.
  • the ratio of Li 2 S to P 2 S 5 in the Li—PS system glass and Li—PS system glass ceramic is a molar ratio of Li 2 S: P 2 S 5 , preferably 65:35 to 85:15, more preferably 68:32 to 77:23.
  • the lithium ion conductivity can be further increased.
  • the lithium ion conductivity can be preferably 1 ⁇ 10 ⁇ 4 S / cm or more, more preferably 1 ⁇ 10 ⁇ 3 S / cm or more. Although there is no particular upper limit, it is practical that it is 1 ⁇ 10 ⁇ 1 S / cm or less.
  • the second sulfide-based inorganic solid electrolyte for example, a compound using a raw material composition containing Li 2 S and a sulfide of an element belonging to Group 13 to Group 15 is used. Can be mentioned.
  • Li 2 S—P 2 S 5 Li 2 S—LiI—P 2 S 5 , Li 2 S—LiI—Li 2 O—P 2 S 5 , Li 2 S—LiBr—P 2 S 5 , Li 2 S—Li 2 O—P 2 S 5 , Li 2 S—Li 3 PO 4 —P 2 S 5 , Li 2 S—P 2 S 5 —P 2 O 5 , Li 2 S—P 2 S 5- SiS 2 , Li 2 S—P 2 S 5 —SnS, Li 2 S—P 2 S 5 —Al 2 S 3 , Li 2 S—GeS 2 , Li 2 S—GeS 2 —ZnS, Li 2 S— Ga 2 S 3 , Li 2 S—GeS 2 —Ga 2 S 3 , Li 2 S—GeS 2 —P 2 S 5 , Li 2 S—GeS 2 —Sb 2 S 5 , Li 2 S—GeS 2 —Al 2 S 3, Li 2 S—S—P
  • Examples of a method for synthesizing a sulfide-based inorganic solid electrolyte material using such a raw material composition include an amorphization method.
  • Examples of the amorphization method include a mechanical milling method and a melt quenching method, and among them, the mechanical milling method is preferable. This is because processing at room temperature is possible, and the manufacturing process can be simplified. Among these, Li 2 S—P 2 S 5 , LGPS (Li 10 GeP 2 S 12 ), Li 2 S—P 2 S 5 —SiS 2 and the like are preferable.
  • the inorganic solid electrolyte is a particle.
  • the average particle size of the particulate inorganic solid electrolyte is not particularly limited, but the average particle size of the first sulfide-based inorganic solid electrolyte and the second sulfide-based inorganic solid electrolyte may both be 0.01 ⁇ m or more. Preferably, it is 0.1 ⁇ m or more. As an upper limit, it is preferable that it is 100 micrometers or less, and it is more preferable that it is 50 micrometers or less.
  • the ratio between the average particle diameter of the first sulfide-based inorganic solid electrolyte and the average particle diameter of the second sulfide-based inorganic solid electrolyte is not particularly limited, but is 0.001: 1 to 1: 1. Preferably, it is 0.001: 1 to 0.5: 1, more preferably 0.01: 1 to 0.5: 1.
  • the measurement of the average particle diameter of an inorganic solid electrolyte can be performed using a scanning electron microscope (SEM) or a transmission electron microscope (TEM), for example.
  • SEM scanning electron microscope
  • TEM transmission electron microscope
  • the electrode sheet for an all-solid secondary battery is observed with an electron microscope, and 100 particles are arbitrarily selected from the primary particles of the inorganic solid electrolyte in the sheet.
  • the average particle diameter of the inorganic solid electrolyte is a value obtained by measuring the horizontal ferret diameter and the vertical ferret diameter of the primary particles and averaging the larger measured value of them. When the horizontal ferret diameter and the vertical ferret diameter are equal, either measurement value may be used.
  • the total content of the first sulfide-based inorganic solid electrolyte and the second sulfide-based inorganic solid electrolyte in the solid electrolyte composition is determined by considering the balance between battery performance, reduction in interface resistance, and maintenance effect.
  • 100% by mass it is preferably 1% by mass or more, more preferably 10% by mass or more, and particularly preferably 20% by mass or more.
  • the upper limit is preferably 99% by mass or less, more preferably 90% by mass or less, and particularly preferably 80% by mass or less.
  • the ratio of the content of the first sulfide-based inorganic solid electrolyte and the content of the second sulfide-based inorganic solid electrolyte is not particularly limited, but is preferably 0.001: 1 to 1: 1, More preferably, the ratio is from 001: 1 to 0.5: 1, and particularly preferably from 0.01: 1 to 0.5: 1.
  • solid content refers to a component that does not volatilize or evaporate when subjected to a drying treatment at 170 ° C. for 6 hours in a nitrogen atmosphere. Typically, it refers to components other than the dispersion medium described below.
  • Each of the first sulfide-based inorganic solid electrolyte and the second sulfide-based inorganic solid electrolyte may be used alone or in combination of two or more.
  • the solid electrolyte composition of the present invention preferably contains a binder.
  • a binder By being contained in the solid electrolyte composition, the inorganic solid electrolyte and the solid particles such as the active material can be firmly bound, and the interfacial resistance between the solid particles can be reduced.
  • a resin may be used as a term having the same meaning as a polymer.
  • the binder used in the present invention is not particularly limited as long as it is an organic polymer.
  • the binder that can be used in the present invention is preferably a binder that is usually used as a binder for a positive electrode active material layer or a negative electrode active material layer of a battery material, and is not particularly limited.
  • a binder made of a resin described below is used. preferable.
  • fluorine-containing resin examples include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), a copolymer of polyvinylidene fluoride and hexafluoropropylene (PVdF-HFP), and the like.
  • hydrocarbon-based thermoplastic resin examples include polyethylene, polypropylene, styrene butadiene rubber (SBR), hydrogenated styrene butadiene rubber (HSBR), butylene rubber, acrylonitrile butadiene rubber, polybutadiene, and polyisoprene.
  • acrylic resin preferably acrylic latex
  • acrylic resin examples include, for example, poly (meth) methyl acrylate, poly (meth) ethyl acrylate, poly (meth) acrylate isopropyl, poly (meth) acrylate isobutyl, and poly (meth) acrylic.
  • examples thereof include acrylic acid, poly (meth) acrylic acid benzyl, poly (meth) acrylic acid glycidyl, poly (meth) acrylic acid dimethylaminopropyl, and a copolymer of monomers constituting these resins. Further, copolymers with other vinyl monomers are also preferably used.
  • Examples thereof include poly (meth) methyl acrylate-polystyrene copolymer, poly (meth) methyl acrylate-acrylonitrile copolymer, poly (meth) acrylate butyl-acrylonitrile-styrene copolymer, and the like.
  • a polycondensation polymer can also be used.
  • the polycondensation polymer for example, urethane resin (preferably urethane latex), urea resin (preferably urea latex), amide resin, imide resin, polyester resin, and the like can be suitably used.
  • the polycondensation polymer preferably has a hard segment part and a soft segment part.
  • the hard segment site indicates a site capable of forming an intermolecular hydrogen bond
  • the soft segment site generally indicates a flexible site having a glass transition temperature (Tg) of room temperature (25 ⁇ 5 ° C.) or lower and a molecular weight of 400 or higher.
  • Tg glass transition temperature
  • a binder may be used individually by 1 type, or may be used in combination of 2 or more type.
  • the upper limit of the glass transition temperature of the binder is preferably 50 ° C. or lower, more preferably 0 ° C. or lower, and particularly preferably ⁇ 20 ° C. or lower.
  • the lower limit is preferably ⁇ 100 ° C. or higher, more preferably ⁇ 70 ° C. or higher, and particularly preferably ⁇ 50 ° C. or higher.
  • the glass transition temperature (Tg) can be measured using a dry sample and a differential scanning calorimeter “X-DSC7000” (trade name, manufactured by SII Nanotechnology) under the following conditions. The measurement is performed twice on the same sample, and the second measurement result is adopted. Measurement chamber atmosphere: Nitrogen (50 mL / min) Temperature increase rate: 5 ° C / min Measurement start temperature: -100 ° C Measurement end temperature: 200 ° C Sample pan: Aluminum pan Mass of measurement sample: 5 mg Calculation of Tg: Tg is calculated by rounding off the decimal point of the intermediate temperature between the lowering start point and the lowering end point of the DSC chart.
  • the water concentration of the polymer constituting the binder used in the present invention is preferably 100 ppm (mass basis) or less, and Tg is preferably 100 ° C. or less.
  • the solvent used for the polymerization reaction of the polymer is not particularly limited. It is desirable to use a solvent that does not react with the inorganic solid electrolyte or the active material and that does not decompose them.
  • hydrocarbon solvents toluene, heptane, xylene
  • ester solvents ethyl acetate, propylene glycol monomethyl ether acetate
  • ether solvents tetrahydrofuran, dioxane, 1,2-diethoxyethane
  • ketone solvents acetone
  • Methyl ethyl ketone Methyl ethyl ketone, cyclohexanone
  • nitrile solvents acetonitrile, propionitrile, butyronitrile, isobutyronitrile
  • halogen solvents dichloromethane, chloroform
  • the polymer constituting the binder used in the present invention preferably has a mass average molecular weight of 10,000 or more, more preferably 20,000 or more, and even more preferably 50,000 or more. As an upper limit, 1,000,000 or less is preferable, 200,000 or less is more preferable, and 100,000 or less is more preferable.
  • the molecular weight of the polymer means a mass average molecular weight unless otherwise specified. The mass average molecular weight can be measured as a molecular weight in terms of polystyrene by gel permeation chromatography (GPC).
  • GPC apparatus HLC-8220 manufactured by Tosoh Corporation
  • the column is G3000HXL + G2000HXL
  • the flow rate is 1 mL / min at 23 ° C.
  • detection is performed by RI.
  • the eluent can be selected from THF (tetrahydrofuran), chloroform, NMP (N-methyl-2-pyrrolidone), m-cresol / chloroform (manufactured by Shonan Wako Pure Chemical Industries, Ltd.). Will be used.
  • the content of the binder in the solid electrolyte composition is 0.01% by mass with respect to 100% by mass of the solid component, considering good reduction in interface resistance and its maintainability when used in an all-solid secondary battery.
  • the above is preferable, 0.1% by mass or more is more preferable, and 1% by mass or more is more preferable.
  • the binder used in the present invention is a polymer particle that retains the particle shape.
  • the “polymer particles” refer to particles that do not completely dissolve even when added to the dispersion medium described later, and are dispersed in the dispersion medium in the form of particles and exhibit an average particle diameter of more than 0.01 ⁇ m.
  • the shape of the polymer particles is not limited as long as they are solid.
  • the polymer particles may be monodispersed or polydispersed.
  • the polymer particles may be spherical or flat and may be amorphous.
  • the surface of the polymer particles may be smooth or may have an uneven shape.
  • the polymer particles may have a core-shell structure, and the core (inner core) and the shell (outer shell) may be made of the same material or different materials. Moreover, it may be hollow and the hollow ratio is not limited.
  • the polymer particles can be synthesized by a method of polymerizing in the presence of a surfactant, an emulsifier or a dispersant, or a method of depositing in a crystalline form as the molecular weight increases. Moreover, you may use the method of crushing the existing polymer mechanically, and the method of making a polymer liquid fine particle by reprecipitation.
  • the average particle diameter of the polymer particles is preferably 0.01 ⁇ m to 100 ⁇ m, more preferably 0.05 ⁇ m to 50 ⁇ m, further preferably 0.1 ⁇ m to 20 ⁇ m, and particularly preferably 0.2 ⁇ m to 10 ⁇ m.
  • the average particle size of the polymer particles used in the present invention shall be based on the measurement conditions and definitions described below.
  • the polymer particles are diluted and prepared in a 20 ml sample bottle using an arbitrary solvent (dispersion medium used in preparing the solid electrolyte composition of the present invention, for example, heptane).
  • the diluted dispersion sample is irradiated with 1 kHz ultrasonic waves for 10 minutes and used immediately after that.
  • a laser diffraction / scattering particle size distribution measuring device LA-920 (trade name, manufactured by HORIBA)
  • data was acquired 50 times using a quartz cell for measurement at a temperature of 25 ° C., Let the obtained volume average particle diameter be an average particle diameter.
  • JISZ8828 2013 “Particle Size Analysis—Dynamic Light Scattering Method” is referred to as necessary. Five samples are prepared for each level and measured, and the average value is adopted. In addition, the measurement from the produced all-solid-state secondary battery is performed, for example, after disassembling the battery and peeling off the electrode, then measuring the electrode material according to the method for measuring the average particle diameter of the polymer particles, This can be done by eliminating the measured value of the average particle diameter of the particles other than the polymer particles that have been measured.
  • a commercial item can be used for the binder used for this invention. Moreover, it can also prepare by a conventional method.
  • the solid electrolyte composition of the present invention contains an active material capable of inserting and releasing ions of metal elements belonging to Group 1 or Group 2 of the periodic table.
  • the active material include a positive electrode active material and a negative electrode active material, and a transition metal oxide that is a positive electrode active material or graphite that is a negative electrode active material is preferable.
  • a solid electrolyte composition containing an active material positive electrode active material, negative electrode active material
  • an electrode layer composition positive electrode layer composition, negative electrode layer composition.
  • the positive electrode active material that may be contained in the solid electrolyte composition of the present invention is preferably one that can reversibly insert and release lithium ions.
  • the material is not particularly limited as long as it has the above characteristics, and may be a transition metal oxide or an element that can be complexed with Li such as sulfur.
  • the positive electrode active material it is preferable to use a transition metal oxide, and a transition metal oxide having a transition metal element M a (one or more elements selected from Co, Ni, Fe, Mn, Cu, and V). More preferred.
  • this transition metal oxide includes an element M b (an element of the first (Ia) group of the metal periodic table other than lithium, an element of the second (IIa) group, Al, Ga, In, Ge, Sn, Pb, Elements such as Sb, Bi, Si, P, and B) may be mixed.
  • the mixing amount is preferably 0 ⁇ 30 mol% relative to the amount of the transition metal element M a (100mol%). Those synthesized by mixing so that the molar ratio of Li / Ma is 0.3 to 2.2 are more preferable.
  • transition metal oxide examples include (MA) a transition metal oxide having a layered rock salt structure, (MB) a transition metal oxide having a spinel structure, (MC) a lithium-containing transition metal phosphate compound, (MD And lithium-containing transition metal halide phosphate compounds, (ME) lithium-containing transition metal silicate compounds, and the like.
  • transition metal oxides having a layered rock salt structure LiCoO 2 (lithium cobaltate [LCO]), LiNiO 2 (lithium nickelate) LiNi 0.85 Co 0.10 Al 0.05 O 2 (Lithium nickel cobalt aluminate [NCA]), LiNi 0.33 Co 0.33 Mn 0.33 O 2 (lithium nickel manganese cobaltate [NMC]), LiNi 0.5 Mn 0.5 O 2 (manganese nickel acid Lithium).
  • (MB) As specific examples of the transition metal oxide having a spinel structure, LiMn 2 O 4, LiCoMnO 4, Li 2 FeMn 3 O 8 , Li 2 CuMn 3 O 8 , Li 2 CrMn 3 O 8, Li 2 NiMn 3 O 8 is mentioned.
  • Examples of (MC) lithium-containing transition metal phosphate compounds include olivine-type iron phosphate salts such as LiFePO 4 and Li 3 Fe 2 (PO 4 ) 3 , iron pyrophosphates such as LiFeP 2 O 7 , LiCoPO 4 and the like. And monoclinic Nasicon type vanadium phosphate salts such as Li 3 V 2 (PO 4 ) 3 (vanadium lithium phosphate).
  • the (MD) lithium-containing transition metal halogenated phosphate compound for example, Li 2 FePO 4 F such fluorinated phosphorus iron salt, Li 2 MnPO 4 hexafluorophosphate manganese salts such as F, Li 2 CoPO 4 F Cobalt fluorophosphates such as
  • Examples of the (ME) lithium-containing transition metal silicate compound include Li 2 FeSiO 4 , Li 2 MnSiO 4 , Li 2 CoSiO 4, and the like.
  • the shape of the positive electrode active material is not particularly limited, but is preferably particulate.
  • the volume average particle diameter (sphere conversion average particle diameter) of the positive electrode active material is not particularly limited.
  • the thickness can be 0.1 to 50 ⁇ m.
  • an ordinary pulverizer or classifier may be used.
  • the positive electrode active material obtained by the firing method may be used after being washed with water, an acidic aqueous solution, an alkaline aqueous solution, or an organic solvent.
  • the volume average particle diameter (sphere-converted average particle diameter) of the positive electrode active material particles can be measured using a laser diffraction / scattering particle size distribution analyzer LA-920 (trade name, manufactured by HORIBA).
  • the positive electrode active materials may be used alone or in combination of two or more.
  • the mass (mg) (weight per unit area) of the positive electrode active material per unit area (cm 2 ) of the positive electrode active material layer is not particularly limited. This can be determined as appropriate according to the designed battery capacity.
  • the content of the positive electrode active material in the solid electrolyte composition is not particularly limited, and is preferably from 10 to 95% by mass, particularly preferably from 20 to 90% by mass, at a solid content of 100% by mass.
  • the negative electrode active material that may be contained in the solid electrolyte composition of the present invention is preferably one that can reversibly insert and release lithium ions.
  • the material is not particularly limited as long as it has the above characteristics, and is a carbonaceous material, a metal oxide such as tin oxide or silicon oxide, a metal composite oxide, a lithium alloy such as lithium simple substance or lithium aluminum alloy, and , Metals such as Sn, Si, and In that can form an alloy with lithium.
  • a carbonaceous material or a lithium composite oxide is preferably used from the viewpoint of reliability.
  • the metal composite oxide is preferably capable of inserting and extracting lithium.
  • the material is not particularly limited, but preferably contains titanium and / or lithium as a constituent component from the viewpoint of high current density charge / discharge characteristics.
  • the carbonaceous material used as the negative electrode active material is a material substantially made of carbon.
  • various synthetics such as petroleum pitch, carbon black such as acetylene black (AB), graphite (natural graphite, artificial graphite such as vapor-grown graphite), PAN (polyacrylonitrile) -based resin, furfuryl alcohol resin, etc.
  • the carbonaceous material which baked resin can be mentioned.
  • various carbon fibers such as PAN-based carbon fiber, cellulose-based carbon fiber, pitch-based carbon fiber, vapor-grown carbon fiber, dehydrated PVA (polyvinyl alcohol) -based carbon fiber, lignin carbon fiber, glassy carbon fiber, activated carbon fiber, etc. And mesophase microspheres, graphite whiskers, flat graphite and the like.
  • an amorphous oxide is particularly preferable, and chalcogenite, which is a reaction product of a metal element and an element of Group 16 of the periodic table, is also preferably used. It is done.
  • amorphous as used herein means an X-ray diffraction method using CuK ⁇ rays, which has a broad scattering band having a peak in the region of 20 ° to 40 ° in terms of 2 ⁇ , and is a crystalline diffraction line. You may have.
  • the strongest intensity of crystalline diffraction lines seen from 2 ° to 40 ° to 70 ° is 100 times the diffraction line intensity at the peak of the broad scattering band seen from 2 ° to 20 °. It is preferable that it is 5 times or less, and it is particularly preferable not to have a crystalline diffraction line.
  • the amorphous oxide of the metalloid element and the chalcogenide are more preferable, and elements of Groups 13 (IIIB) to 15 (VB) of the periodic table, Al , Ga, Si, Sn, Ge, Pb, Sb, Bi alone or in combination of two or more thereof, and chalcogenide are particularly preferable.
  • preferable amorphous oxides and chalcogenides include, for example, Ga 2 O 3 , SiO, GeO, SnO, SnO 2 , PbO, PbO 2 , Pb 2 O 3 , Pb 2 O 4 , Pb 3 O 4 , Sb 2 O 3 , Sb 2 O 4 , Sb 2 O 5 , Bi 2 O 3 , Bi 2 O 4 , SnSiO 3 , GeS, SnS, SnS 2 , PbS, PbS 2 , Sb 2 S 3 , Sb 2 S 5 , SnSiS 3 is preferred.
  • these may be a complex oxide with lithium oxide, for example, Li 2 SnO 2 .
  • the negative electrode active material contains a titanium atom. More specifically, Li 4 Ti 5 O 12 (lithium titanate [LTO]) is excellent in rapid charge / discharge characteristics due to small volume fluctuations during occlusion and release of lithium ions, and the deterioration of the electrode is suppressed, and the lithium ion secondary This is preferable in that the battery life can be improved.
  • Li 4 Ti 5 O 12 lithium titanate [LTO]
  • hard carbon or graphite is preferably used, and graphite is more preferably used.
  • the carbonaceous materials may be used singly or in combination of two or more.
  • the shape of the negative electrode active material is not particularly limited, but is preferably particulate.
  • the average particle size of the negative electrode active material is preferably 0.1 to 60 ⁇ m.
  • a normal pulverizer or classifier is used.
  • a mortar, a ball mill, a sand mill, a vibrating ball mill, a satellite ball mill, a planetary ball mill, a swirling air flow type jet mill or a sieve is preferably used.
  • wet pulverization in the presence of water or an organic solvent such as methanol can be performed as necessary.
  • classification is preferably performed.
  • the classification method is not particularly limited, and a sieve, an air classifier, or the like can be used as necessary. Classification can be used both dry and wet.
  • the average particle diameter of the negative electrode active material particles can be measured by the same method as the above-described method for measuring the volume average particle diameter of the positive electrode active material.
  • the chemical formula of the compound obtained by the above firing method can be calculated from an inductively coupled plasma (ICP) emission spectroscopic analysis method as a measurement method, and from a mass difference between powders before and after firing as a simple method.
  • ICP inductively coupled plasma
  • a negative electrode active material that can be used in combination with an amorphous oxide negative electrode active material centering on Sn, Si, Ge, a carbonaceous material capable of inserting and extracting lithium ions or lithium metal, lithium, lithium alloy, A metal that can be alloyed with lithium is preferable.
  • a Si-based negative electrode it is also preferable to apply a Si-based negative electrode.
  • a Si negative electrode can occlude more Li ions than a carbon negative electrode (graphite, acetylene black, etc.). That is, the amount of Li ion occlusion per unit weight increases. Therefore, the battery capacity can be increased. As a result, there is an advantage that the battery driving time can be extended.
  • the said negative electrode active material may be used individually by 1 type, or may be used in combination of 2 or more type.
  • the mass (mg) (weight per unit area) of the negative electrode active material per unit area (cm 2 ) of the negative electrode active material layer is not particularly limited. This can be determined as appropriate according to the designed battery capacity.
  • the content of the negative electrode active material in the solid electrolyte composition is not particularly limited, and is preferably 10 to 95% by mass, and particularly preferably 20 to 90% by mass with a solid content of 100% by mass.
  • the solid electrolyte composition of the present invention preferably contains a dispersion medium.
  • the dispersion medium only needs to disperse each of the above components, and examples thereof include various organic solvents. Specific examples of the dispersion medium include the following.
  • Examples of the alcohol compound solvent include methyl alcohol, ethyl alcohol, 1-propyl alcohol, 2-propyl alcohol, 2-butanol, ethylene glycol, propylene glycol, glycerin, 1,6-hexanediol, cyclohexanediol, sorbitol, xylitol, Examples include 2-methyl-2,4-pentanediol, 1,3-butanediol, and 1,4-butanediol.
  • ether compound solvents examples include alkylene glycol alkyl ethers (ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol, dipropylene glycol, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol, polyethylene glycol, propylene glycol monomethyl ether, dipropylene.
  • alkylene glycol alkyl ethers ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol, dipropylene glycol, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol, polyethylene glycol, propylene glycol monomethyl ether, dipropylene.
  • Glycol monomethyl ether tripropylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether, etc.
  • dialkyl ethers dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, etc.
  • cyclic ethers tetrahydrofuran, geo Sun (1,2, including 1,3- and 1,4-isomers of), etc.
  • Examples of the amide compound solvent include N, N-dimethylformamide, N-methyl-2-pyrrolidone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, 2-pyrrolidinone, ⁇ -caprolactam, formamide, N -Methylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropanamide, hexamethylphosphoric triamide and the like.
  • Examples of the amino compound solvent include triethylamine, diisopropylethylamine, tributylamine and the like.
  • Examples of the ketone compound solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.
  • Examples of the aromatic compound solvent include benzene, toluene, xylene and the like.
  • Examples of the aliphatic compound solvent include hexane, heptane, octane, decane, and the like.
  • Examples of the nitrile compound solvent include acetonitrile, propyronitrile, isobutyronitrile, and the like.
  • Examples of the ester compound solvent include ethyl acetate, butyl acetate, propyl acetate, butyl butyrate, and butyl pentanoate.
  • Examples of the non-aqueous dispersion medium include the above aromatic compound solvents and aliphatic compound solvents.
  • the solid electrolyte composition of the present invention may appropriately contain a conductive aid used for improving the electronic conductivity of the active material, as necessary.
  • a conductive aid used for improving the electronic conductivity of the active material
  • a general conductive auxiliary agent can be used.
  • graphites such as natural graphite and artificial graphite, carbon blacks such as acetylene black, ketjen black and furnace black, amorphous carbon such as needle coke, vapor-grown carbon fiber and carbon nanotubes, which are electron conductive materials
  • Carbon fibers such as graphene, carbonaceous materials such as graphene and fullerene, metal powders such as copper and nickel, and metal fibers may be used, and conductive polymers such as polyaniline, polypyrrole, polythiophene, polyacetylene, and polyphenylene derivatives May be used.
  • 1 type of these may be used and 2 or more types may be used.
  • the content of the conductive auxiliary in the solid electrolyte composition of the present invention
  • the solid electrolyte composition of the present invention preferably contains a lithium salt.
  • a lithium salt the lithium salt normally used for this kind of product is preferable and there is no restriction
  • the content of the lithium salt is preferably 0 parts by mass or more, more preferably 5 parts by mass or more with respect to 100 parts by mass of the solid electrolyte.
  • As an upper limit 50 mass parts or less are preferable, and 20 mass parts or less are more preferable.
  • the solid electrolyte composition of the present invention may contain a dispersant.
  • a dispersant By adding the dispersant, even when the concentration of either the electrode active material or the inorganic solid electrolyte is high, the aggregation can be suppressed and a uniform active material layer can be formed.
  • the dispersant those usually used for all-solid secondary batteries can be appropriately selected and used. For example, it is composed of a low molecule or oligomer having a molecular weight of 200 or more and less than 3,000, and a functional group represented by the functional group (I) and an alkyl group having 8 or more carbon atoms or an aryl group having 10 or more carbon atoms in the same molecule. What is contained is preferable.
  • the content of the dispersant in the layer is preferably 0.2 to 10% by mass.
  • the method for bringing the active material into contact with the first sulfide-based inorganic solid electrolyte is not particularly limited.
  • the active material is put into a solution in which the first sulfide-based inorganic solid electrolyte is dissolved in the dispersion medium, and stirred at room temperature (20 ° C. to 30 ° C.) for 1 to 60 minutes. Thereafter, the active material and the first sulfide-based inorganic solid electrolyte can be brought into contact with each other by drying at 80 ° C. to 300 ° C. for 0.5 to 5 hours under reduced pressure.
  • the solid electrolyte composition of the present invention comprises an active material in contact with the first sulfide-based inorganic solid electrolyte, a second sulfide-based inorganic solid electrolyte, and optionally other components such as binder particles and a dispersion medium. Can be prepared by mixing or adding.
  • the aspect in which the first sulfide-based inorganic solid electrolyte is in contact with the active material is not particularly limited.
  • the first sulfide-based inorganic solid electrolyte may be uniform or non-uniform on all or part of the active material surface.
  • covers uniformly is mentioned.
  • the mixing of the above components can be performed using, for example, various mixers.
  • the mixing conditions are not particularly limited, and examples thereof include a ball mill, a bead mill, a planetary mixer, a blade mixer, a roll mill, a kneader, and a disk mill.
  • seat for all-solid-state secondary batteries is a sheet
  • a sheet preferably used for a solid electrolyte layer also referred to as a solid electrolyte sheet for an all-solid secondary battery
  • a sheet preferably used for an electrode or a laminate of an electrode and a solid electrolyte layer an electrode sheet for an all-solid secondary battery
  • Etc a sheet preferably used for an all-solid secondary battery
  • these various sheets may be collectively referred to as an all-solid secondary battery sheet.
  • the all-solid-state secondary battery sheet used in the present invention is a sheet having a solid electrolyte layer or an active material layer (electrode layer) on a substrate.
  • the all-solid-state secondary battery sheet may have other layers as long as it has a substrate and a solid electrolyte layer or an active material layer. It classifies into a secondary battery electrode sheet. Examples of other layers include a protective layer, a current collector, and a coat layer (current collector, solid electrolyte layer, active material layer) and the like.
  • Examples of the solid electrolyte sheet for an all-solid secondary battery used in the present invention include a sheet having a solid electrolyte layer and a protective layer in this order on a substrate.
  • the substrate is not particularly limited as long as it can support the solid electrolyte layer, and examples thereof include the materials described in the above current collector, sheet materials (plate bodies) such as organic materials and inorganic materials.
  • sheet materials such as organic materials and inorganic materials.
  • organic material include various polymers, and specific examples include polyethylene terephthalate, polypropylene, polyethylene, and cellulose.
  • inorganic material include glass and ceramic.
  • the configuration and layer thickness of the solid electrolyte layer of the all-solid secondary battery sheet are the same as the configuration and layer thickness of the solid electrolyte layer described in the all-solid secondary battery of the present invention.
  • This sheet forms a solid electrolyte layer on a substrate by forming (applying and drying) a solid electrolyte composition for forming a solid electrolyte layer on the substrate (may be through another layer). Is obtained.
  • the solid electrolyte composition for forming the solid electrolyte layer is also referred to as “solid electrolyte layer composition”.
  • the electrode sheet for an all-solid-state secondary battery of the present invention is an electrode sheet having an active material layer on a current collector.
  • This electrode sheet is usually a sheet having a current collector and an active material layer, but an embodiment having a current collector, an active material layer, and a solid electrolyte layer in this order, and a current collector, an active material layer, and a solid electrolyte
  • the aspect which has a layer and an active material layer in this order is also included.
  • the configuration and the layer thickness of each layer constituting the electrode sheet are the same as the configuration and the layer thickness of each layer described in the all solid state secondary battery of the present invention.
  • the electrode sheet is obtained by forming (coating and drying) the solid electrolyte composition containing the active material of the present invention on a metal foil to form an active material layer on the metal foil.
  • Manufacture of all-solid-state secondary battery and electrode sheet for all-solid-state secondary battery can be performed by a conventional method. Specifically, the all-solid-state secondary battery and the electrode sheet for the all-solid-state secondary battery can be manufactured by forming each of the above layers using the solid electrolyte composition of the present invention. This will be described in detail below.
  • the all-solid-state secondary battery of the present invention is produced by a method including (intervening) the step of applying the solid electrolyte composition of the present invention onto a metal foil to be a current collector and forming (forming) a coating film.
  • a positive electrode active material layer is formed by applying a solid electrolyte composition containing a positive electrode active material as a positive electrode material (positive electrode layer composition) on a metal foil that is a positive electrode current collector.
  • a positive electrode sheet for a secondary battery is prepared.
  • a solid electrolyte composition for forming a solid electrolyte layer is applied on the positive electrode active material layer to form a solid electrolyte layer.
  • a solid electrolyte composition containing a negative electrode active material is applied as a negative electrode material (negative electrode layer composition) on the solid electrolyte layer to form a negative electrode active material layer.
  • An all-solid secondary battery having a structure in which a solid electrolyte layer is sandwiched between a positive electrode active material layer and a negative electrode active material layer is obtained by stacking a negative electrode current collector (metal foil) on the negative electrode active material layer. Can do. If necessary, this can be enclosed in a housing to obtain a desired all-solid secondary battery.
  • the solid electrolyte composition for forming the solid electrolyte layer is not particularly limited, and a normal one can be used.
  • the component which the solid electrolyte composition for forming a solid electrolyte layer contains may be the same as the component which the solid electrolyte composition of this invention contains.
  • the solid electrolyte composition for forming the solid electrolyte layer does not contain an active material.
  • the formation method of each layer is reversed, and a negative electrode active material layer, a solid electrolyte layer, and a positive electrode active material layer are formed on the negative electrode current collector, and the positive electrode current collector is stacked to manufacture an all-solid secondary battery. You can also
  • Another method includes the following method. That is, a positive electrode sheet for an all-solid secondary battery is produced as described above. In addition, a solid electrolyte composition containing a negative electrode active material is applied as a negative electrode material (a composition for a negative electrode layer) on a metal foil that is a negative electrode current collector to form a negative electrode active material layer. A negative electrode sheet for a secondary battery is prepared. Next, a solid electrolyte layer is formed on one of the active material layers of these sheets as described above. Furthermore, the other of the positive electrode sheet for an all solid secondary battery and the negative electrode sheet for an all solid secondary battery is laminated on the solid electrolyte layer so that the solid electrolyte layer and the active material layer are in contact with each other.
  • Another method includes the following method. That is, as described above, a positive electrode sheet for an all-solid secondary battery and a negative electrode sheet for an all-solid secondary battery are produced. Separately from this, a solid electrolyte composition is applied on a substrate to produce a solid electrolyte sheet for an all-solid secondary battery comprising a solid electrolyte layer. Furthermore, it laminates
  • An all-solid-state secondary battery can also be manufactured by a combination of the above forming methods. For example, as described above, a positive electrode sheet for an all-solid secondary battery, a negative electrode sheet for an all-solid secondary battery, and a solid electrolyte sheet for an all-solid secondary battery are produced. Then, after laminating the solid electrolyte layer peeled off from the base material on the negative electrode sheet for an all solid secondary battery, an all solid secondary battery can be produced by pasting the positive electrode sheet for the all solid secondary battery. it can. In this method, the solid electrolyte layer can be laminated on the positive electrode sheet for an all-solid secondary battery, and bonded to the negative electrode sheet for an all-solid secondary battery.
  • the method for applying the solid electrolyte composition is not particularly limited, and can be appropriately selected. Examples thereof include coating (preferably wet coating), spray coating, spin coating coating, dip coating, slit coating, stripe coating, and bar coating coating. At this time, the solid electrolyte composition may be dried after being applied, or may be dried after being applied in multiple layers.
  • the drying temperature is not particularly limited.
  • the lower limit is preferably 30 ° C or higher, more preferably 60 ° C or higher, and still more preferably 80 ° C or higher.
  • the upper limit is preferably 300 ° C. or lower, more preferably 250 ° C. or lower, and further preferably 200 ° C. or lower.
  • a dispersion medium By heating in such a temperature range, a dispersion medium can be removed and it can be set as a solid state. Moreover, it is preferable because the temperature is not excessively raised and each member of the all-solid-state secondary battery is not damaged. Thereby, in the all-solid-state secondary battery, excellent overall performance is exhibited, and good binding properties and good ionic conductivity can be obtained even without pressure.
  • each layer or all-solid secondary battery After producing the applied solid electrolyte composition or all-solid-state secondary battery. Moreover, it is also preferable to pressurize in the state which laminated
  • An example of the pressurizing method is a hydraulic cylinder press.
  • the applied pressure is not particularly limited and is generally preferably in the range of 50 to 1500 MPa. Moreover, you may heat the apply
  • the heating temperature is not particularly limited, and is generally in the range of 30 to 300 ° C. It is also possible to press at a temperature higher than the glass transition temperature of the inorganic solid electrolyte.
  • pressing can be performed at a temperature higher than the glass transition temperature of the polymer forming the binder particles.
  • the temperature does not exceed the melting point of the polymer.
  • the pressurization may be performed in a state where the coating solvent or the dispersion medium is previously dried, or may be performed in a state where the solvent or the dispersion medium remains.
  • the atmosphere during pressurization is not particularly limited, and may be any of the following: air, dry air (dew point of ⁇ 20 ° C. or lower), inert gas (for example, argon gas, helium gas, nitrogen gas).
  • the pressing time may be a high pressure in a short time (for example, within several hours), or a medium pressure may be applied for a long time (1 day or more).
  • a restraining tool screw tightening pressure or the like
  • the pressing pressure may be uniform or different with respect to the pressed part such as the sheet surface.
  • the pressing pressure can be changed according to the area and film thickness of the pressed part. Also, the same part can be changed stepwise with different pressures.
  • the press surface may be smooth or roughened.
  • the all solid state secondary battery manufactured as described above is preferably initialized after manufacture or before use.
  • the initialization is not particularly limited, and can be performed, for example, by performing initial charging / discharging in a state where the press pressure is increased, and then releasing the pressure until the general use pressure of the all-solid secondary battery is reached.
  • the all solid state secondary battery of the present invention can be applied to various uses. Although there is no particular limitation on the application mode, for example, when installed in an electronic device, a notebook computer, a pen input personal computer, a mobile personal computer, an electronic book player, a mobile phone, a cordless phone, a pager, a handy terminal, a mobile fax machine, a mobile phone Copy, portable printer, headphone stereo, video movie, LCD TV, handy cleaner, portable CD, minidisc, electric shaver, transceiver, electronic notebook, calculator, portable tape recorder, radio, backup power supply, memory card, etc.
  • Other consumer products include automobiles, electric vehicles, motors, lighting equipment, toys, game equipment, road conditioners, watches, strobes, cameras, medical equipment (such as pacemakers, hearing aids, and shoulder grinders). Furthermore, it can be used for various military purposes and space. Moreover, it can also combine with a solar cell.
  • An all-solid secondary battery is a secondary battery in which the positive electrode, the negative electrode, and the electrolyte are all solid. In other words, it is distinguished from an electrolyte type secondary battery using a carbonate-based solvent as an electrolyte.
  • this invention presupposes an inorganic all-solid-state secondary battery.
  • the all-solid-state secondary battery includes an organic (polymer) all-solid-state secondary battery that uses a polymer compound such as polyethylene oxide as an electrolyte, and an inorganic all-solid-state secondary battery that uses the above-described Li-PS-based glass ceramics. It is divided into and.
  • the inorganic solid electrolyte is distinguished from the above-described electrolyte (polymer electrolyte) using a polymer compound such as polyethylene oxide as an ion conductive medium, and the inorganic compound serves as an ion conductive medium. Specific examples include the Li—PS—S glass ceramics described above.
  • the inorganic solid electrolyte itself does not release cations (Li ions) but exhibits an ion transport function.
  • a material that is added to the electrolytic solution or the solid electrolyte layer and serves as a source of ions that release cations is sometimes called an electrolyte, but it is distinguished from the electrolyte as the ion transport material.
  • electrolyte salt or “supporting electrolyte”.
  • the electrolyte salt include LiTFSI (lithium bistrifluoromethanesulfonylimide).
  • composition means a mixture in which two or more components are uniformly mixed. However, as long as the uniformity is substantially maintained, aggregation or uneven distribution may partially occur within a range in which a desired effect is achieved.
  • a solid electrolyte composition when it is referred to as a solid electrolyte composition, it basically refers to a composition (typically a paste) that is a material for forming a solid electrolyte layer or the like, and an electrolyte layer or the like formed by curing the composition. Shall not be included in this.
  • Li 6 PS 5 Cl> In a glove box under an argon atmosphere (dew point -70 ° C.), lithium sulfide (Li 2 S, Aldrich Corp., purity> 99.98%) 0.43 g, diphosphorus pentasulfide (P 2 S 5, Aldrich Co. , Purity> 99%) 0.41 g and lithium chloride (LiCl, manufactured by Aldrich, purity> 99%) 0.16 g were weighed, put into an agate mortar, and using an agate pestle for 5 minutes at room temperature. Mixed.
  • Li 6 PS 5 Br> In a glove box under an argon atmosphere (dew point ⁇ 70 ° C.), 0.37 g of lithium sulfide (Li 2 S, manufactured by Aldrich, purity> 99.98%), diphosphorus pentasulfide (P 2 S 5 , manufactured by Aldrich) , Purity> 99%) 0.35 g and lithium bromide (LiBr, manufactured by Aldrich, purity> 99%) 0.28 g were weighed, put into an agate mortar, and 5 at room temperature using an agate pestle. Mixed for minutes.
  • Ten zirconia beads having a diameter of 10 mm were introduced into a 45 mL container (made by Fritsch) made of zirconia, the whole mixture of lithium sulfide, diphosphorus pentasulfide and lithium bromide was introduced, and the container was sealed under an argon atmosphere. .
  • a container is set in a planetary ball mill P-7 (trade name) manufactured by Fricht Co., and mechanical milling is performed at a temperature of 25 ° C. and a rotation speed of 600 rpm for 10 hours.
  • the first sulfide-based inorganic solid electrolyte Li 6 PS 5 containing a crystal phase 1.00 g of Br was obtained.
  • Li 6 PS 5 I> In a glove box under an argon atmosphere (dew point ⁇ 70 ° C.), 0.32 g of lithium sulfide (Li 2 S, manufactured by Aldrich, purity> 99.98%), diphosphorus pentasulfide (P 2 S 5 , manufactured by Aldrich) , Purity> 99%) 0.31 g and lithium iodide (LiI, manufactured by Aldrich, purity> 99%) 0.37 g were weighed, put into an agate mortar, and 5 hours at room temperature using an agate pestle. Mixed for minutes.
  • Ten zirconia beads having a diameter of 10 mm were introduced into a 45 mL container (made by Fritsch) made of zirconia, the whole mixture of lithium sulfide, diphosphorus pentasulfide and lithium iodide was introduced, and the container was sealed under an argon atmosphere. .
  • a container is set in a planetary ball mill P-7 (trade name) manufactured by Fricht Co., and mechanical milling is performed at a temperature of 25 ° C. and a rotation speed of 600 rpm for 10 hours.
  • the first sulfide-based inorganic solid electrolyte Li 6 PS 5 containing a crystal phase 1.00 g of I was obtained.
  • Li 7 GeS 5 Cl> In a glove box under an argon atmosphere (dew point -70 ° C.), 0.43 g of lithium sulfide (Li 2 S, manufactured by Aldrich, purity> 99.98%), germanium sulfide (GeS 2 , manufactured by Aldrich, purity> 99) .99%) 0.43 g and lithium chloride (LiCl, manufactured by Aldrich, purity> 99%) 0.13 g were weighed, put into an agate mortar, and mixed for 5 minutes at room temperature using an agate pestle. .
  • Ten zirconia beads having a diameter of 10 mm were introduced into a 45 mL container (manufactured by Fritsch), and the entire mixture of lithium sulfide, diphosphorus pentasulfide and lithium chloride was introduced, and the container was sealed under an argon atmosphere.
  • a container is set in a planetary ball mill P-7 (trade name) manufactured by Frichtu, and mechanical milling is performed at a temperature of 25 ° C. and a rotation speed of 600 rpm for 10 hours.
  • the first sulfide-based inorganic solid electrolyte Li 7 GeS 5 containing a crystal phase 0.99 g of Cl was obtained.
  • Li 7 SiS 5 Cl> In a glove box under an argon atmosphere (dew point -70 ° C.), 0.51 g of lithium sulfide (Li 2 S, manufactured by Aldrich, purity> 99.98%), silicon sulfide (SiS 2 , manufactured by Wako Pure Chemical Industries, Ltd., purity) > 95%) 0.34 g and lithium chloride (LiCl, manufactured by Aldrich, purity> 99%) 0.16 g were weighed, put into an agate mortar, and mixed for 5 minutes at room temperature using an agate pestle. .
  • Li 2 S lithium sulfide
  • SiS 2 silicon sulfide
  • LiCl lithium chloride
  • Li 7 SnS 5 Cl> In a glove box under an argon atmosphere (dew point ⁇ 70 ° C.), 0.39 g of lithium sulfide (Li 2 S, manufactured by Aldrich, purity> 99.98%), tin sulfide (SnS 2 , manufactured by Rare Metallic, purity> 99.999%) 0.51 g and lithium chloride (LiCl, Aldrich, purity> 99%) 0.12 g were weighed, put into an agate mortar, and mixed for 5 minutes at room temperature using an agate pestle. did.
  • Ten zirconia beads having a diameter of 10 mm were introduced into a 45 mL container (manufactured by Fritsch), and the entire mixture of lithium sulfide, diphosphorus pentasulfide and lithium chloride was introduced, and the container was sealed under an argon atmosphere.
  • a container is set in a planetary ball mill P-7 (trade name) manufactured by Frichtu, and mechanical milling is performed at a temperature of 25 ° C. and a rotation speed of 600 rpm for 10 hours.
  • the first sulfide-based inorganic solid electrolyte Li 7 SnS 5 containing a crystalline phase 1.02 g of Cl was obtained.
  • 66 zirconia beads having a diameter of 5 mm were introduced into a 45 mL container (manufactured by Fritsch) made of zirconia, the whole mixture of lithium sulfide and phosphorous pentasulfide was introduced, and the container was sealed under an argon atmosphere.
  • a container is set in a planetary ball mill P-7 (trade name) manufactured by Frichtu, and mechanical milling is performed at a temperature of 25 ° C. and a rotation speed of 510 rpm for 20 hours.
  • a second sulfide-based inorganic solid electrolyte (Li— 6.20 g of PS glass) was obtained.
  • 66 zirconia beads having a diameter of 5 mm were introduced into a 45 mL container (manufactured by Fritsch) made of zirconia, the whole mixture of lithium sulfide and phosphorous pentasulfide was introduced, and the container was sealed under an argon atmosphere.
  • the container was set in a planetary ball mill P-7 (trade name) manufactured by Frichtu, and mechanical milling was performed at a temperature of 25 ° C. and a rotation speed of 510 rpm for 20 hours.
  • the obtained powder was heated at 300 ° C. for 5 hours under an argon atmosphere to obtain 8.1 g of a first sulfide-based inorganic solid electrolyte Li—PS—based glass ceramic containing a crystal phase.
  • Example 1 Coating of active material with first sulfide-based inorganic solid electrolyte> 0.2g of Li 6 PS 5 Cl (the first sulfide-based inorganic solid electrolyte) dissolved at room temperature in ethanol 1.8g, obtain an ethanol solution of Li 6 PS 5 Cl dissolved. 1.93 g of NMC (LiNi 0.33 Co 0.33 Mn 0.33 O 2 nickel manganese cobalt oxide) as a positive electrode active material was added to 0.4 g of the above solution, stirred at room temperature for 10 minutes, and stirred at 180 ° C. for 3 minutes. The active material coated with the first sulfide-based inorganic solid electrolyte was obtained by drying for a period of time.
  • NMC LiNi 0.33 Co 0.33 Mn 0.33 O 2 nickel manganese cobalt oxide
  • composition for solid electrolyte layer 180 zirconia beads with a diameter of 5 mm were put into a 45 mL container (made by Fritsch) made of zirconia, 9.8 g of the Li—PS glass based on the above synthesis, and the trade name Flow Beads manufactured by Sumitomo Seika Co., Ltd. 0.2 g of LE-1080 (particle shape binder) and 15.0 g of isobutyronitrile as a dispersion medium were added. Thereafter, the container was set on a planetary ball mill P-7 manufactured by Fritsch, and stirring was continued for 2 hours at a temperature of 25 ° C. and a rotation speed of 300 rpm to prepare a composition for a solid electrolyte layer.
  • composition for positive electrode layer a positive electrode layer composition for preparing a positive electrode sheet for an all-solid-state secondary battery was prepared. 180 zirconia beads with a diameter of 5 mm are placed in a 45 mL zirconia container (manufactured by Fritsch), 2 g of the Li—PS system glass (second sulfide-based inorganic solid electrolyte) synthesized above, and Sumitomo Seiko as a binder The trade name Flow Beads LE-1080 manufactured by Kasei Co., Ltd. and 12.3 g of isobutyronitrile were added as a dispersion medium.
  • the container is set in a planetary ball mill P-7 manufactured by Frichtu, and mixing is continued for 2 hours at a temperature of 25 ° C. and a rotation speed of 300 rpm. Then, the active material coated with the first sulfide-based inorganic solid electrolyte is charged into the container. Similarly, a container was set in the planetary ball mill P-7, and mixing was continued at a temperature of 25 ° C. and a rotation speed of 200 rpm for 15 minutes to prepare a positive electrode layer composition.
  • covered with the 1st sulfide type inorganic solid electrolyte, the binder, and the 2nd sulfide type inorganic solid electrolyte was adjusted so that it might become the mass% of Table 1.
  • composition for negative electrode layer a negative electrode layer composition for preparing a negative electrode sheet for an all-solid-state secondary battery was prepared.
  • 180 zirconia beads having a diameter of 5 mm were put into a 45 mL container (manufactured by Fritsch) made of zirconia, 4 g of the Li—PS glass synthesized as described above, and the trade name Flow Beads LE— manufactured by Sumitomo Seika Co., Ltd. 1080. 12.3 g of isobutyronitrile was added as a dispersion medium.
  • the container is set in a planetary ball mill P-7 manufactured by Frichtu, and after mixing for 2 hours at a temperature of 25 ° C.
  • composition for positive electrode layer prepared above was applied onto an aluminum foil having a thickness of 20 ⁇ m by an applicator (trade name: SA-201 Baker type applicator, manufactured by Tester Sangyo Co., Ltd.), heated at 80 ° C. for 1 hour, and further treated with 110 Dry at 1 ° C. for 1 hour. Then, using a heat press machine, it pressurized (600 MPa, 1 minute), heating (120 degreeC), and produced the positive electrode sheet for all-solid-state secondary batteries which has a laminated structure of a positive electrode active material layer / aluminum foil.
  • an applicator trade name: SA-201 Baker type applicator, manufactured by Tester Sangyo Co., Ltd.
  • the negative electrode layer composition prepared above was applied onto a copper foil having a thickness of 20 ⁇ m with an applicator (trade name: SA-201 baker type applicator, manufactured by Tester Sangyo Co., Ltd.), heated at 80 ° C. for 1 hour, and further 110 Dry at 1 ° C. for 1 hour. Then, using a heat press machine, it pressurized (600 MPa, 1 minute), heating (120 degreeC), and produced the negative electrode sheet for all the solid secondary batteries which has a laminated structure of a negative electrode active material layer / copper foil.
  • an applicator trade name: SA-201 baker type applicator, manufactured by Tester Sangyo Co., Ltd.
  • the solid electrolyte layer composition prepared above was applied on the negative electrode active material layer prepared above with an applicator, heated at 80 ° C. for 1 hour, and further heated at 110 ° C. for 6 hours.
  • the sheet having the solid electrolyte layer formed on the negative electrode active material layer was pressurized (600 MPa, 1 minute) while being heated (120 ° C.) using a heat press machine, and the solid electrolyte layer / negative electrode active material layer / copper foil A negative electrode sheet for an all-solid secondary battery having a laminated structure was produced.
  • the all-solid-state secondary battery sheet in the 2032 type coin case has the configuration shown in FIG. 1, and the all-solid-state secondary battery negative electrode sheet (copper foil / negative-electrode active material layer) / solid electrolyte layer / all-solid-state secondary battery use. It has a laminated structure of positive electrode sheets (positive electrode active material layer / aluminum foil). The thicknesses of the positive electrode active material layer, the negative electrode active material layer, and the solid electrolyte layer were 45 ⁇ m, 30 ⁇ m, and 40 ⁇ m, respectively.
  • Examples 2 to 12 and Comparative Examples 1 to 5 All-solid secondary batteries of Examples 2 to 12 and Comparative Examples 1 to 5 were produced in the same manner as the coin battery of Example 1, except that the composition shown in Table 1 below was used.
  • the ratios of the active material, the first sulfide-based inorganic solid electrolyte, the second sulfide-based inorganic solid electrolyte, and the binder were adjusted to be mass% shown in Table 1.
  • the positive electrode layer or negative electrode layer composition used in the examples and comparative examples in which the second electrolyte is described is the same as the positive electrode layer composition of Example 1, It was prepared using an active material coated with a sulfide-based inorganic solid electrolyte.
  • the composition for the positive electrode layer or the negative electrode layer used in Examples and Comparative Examples in which the second electrolyte is not described is obtained by coating the active material with the first sulfide-based inorganic solid electrolyte. It was prepared in the same manner as the negative electrode layer composition of Example 1.
  • the 1st electrolyte in the positive electrode sheet for all-solid-state secondary batteries of the following Table 1 comparative example 3 will decompose
  • NMC LiNi 0.33 Co 0.33 Mn 0.33 O 2 nickel manganese cobalt oxide
  • Li-PS-based glass ceramic first sulfide-based inorganic solid electrolyte
  • the container was set in a planetary ball mill P-7 (trade name) manufactured by Frichtu, and mechanical milling was performed at a temperature of 25 ° C. and a rotation speed of 100 rpm for 30 minutes.
  • the obtained powder was heated at 180 ° C. for 3 hours under an argon atmosphere.
  • Example ratio Comparative example First electrolyte: first sulfide-based inorganic solid electrolyte Second electrolyte: second sulfide-based inorganic solid electrolyte latex system: described in JP-A-2015-88486 [0127]
  • B-1 Ceramic Li-PS-based glass ceramic glass synthesized above: Li-PS-based glass synthesized above In Comparative Examples 1 to 5, glass ceramic and glass were used for comparison with Examples. It is described in the column of 1 electrolyte.

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PCT/JP2017/004029 2016-02-19 2017-02-03 固体電解質組成物、全固体二次電池用電極シートおよび全固体二次電池、並びに、全固体二次電池用電極シートおよび全固体二次電池の製造方法 WO2017141735A1 (ja)

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EP17752997.1A EP3419098B1 (de) 2016-02-19 2017-02-03 Feste elektrolytische zusammensetzung, elektrodenschicht für festkörper-sekundärbatterien, festkörper-sekundärbatterie und verfahren zur herstellung einer elektrodenschicht für festkörper-sekundärbatterien und festkörper-sekundärbatterie
CN201780005815.0A CN108475817B (zh) 2016-02-19 2017-02-03 固体电解质组合物及全固态二次电池的制造方法
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